Condensation of hydrocarbons with carbohydrates and related materials



M g a- States CONDENSATION OF HYDROCONS WITH lgIA AliBsOHYDRATEt ANDRELATED MATE- Carl B. Linn, Riverside, 11]., assignor to Universal 0i!Products Company, Des Plaines, 11]., a corporation of Delaware NoDrawing. Application June 10, 1953, Serial No. 360,838

13 Claims. (Cl. 260 618) This application is a continuation-in-part ofmy copendby condensing hydrocarbons with carbohydrates or with 9carbohydrate derivatives.

One embodiment of this invention relates to a process which comprisescondensing a hydrocarbon with a carbohydrate in the presence of ahydrogen fluoride catalyst, and recovering the resultant condensationproducts.

Another embodiment of this invention relates to a process whichcomprises condensing an isoparaldnic hydrocarbon with a carbohydrate inthe presence of a hydrogen fluoride catalyst, and recovering theresultant condensation products.

Still another embodiment of this invention relates to a process whichcomprises condensing an olefinic hydrocarbon with a carbohydrate in thepresence of a hydrogen fluoride catalyst, and recovering the resultantcondensation products.

Still another embodiment of this invention relates to a process whichcomprises condensing an aromatic hydrocarbon with a carbohydrate in thepresence of a hydrogen fluoride catalyst, and recovering the resultantcondensation products.

A still further embodiment of this invention relates to a process whichcomprises condensing a naphthenic hydrocarbon with a carbohydrate in thepresence of a hydrogen fluoride catalyst, and recovering the resultantcondensation products.

I have found that useful water insoluble condensation r products andalso water soluble condensation products are formed by reactinghydrocarbons with carbohydrates and related substances in the presenceof a hydrogen fluoride catalyst. These reactions may be carried out insteel equipment or other suitable apparatus lined with silver, copper,and certain alloys such as Monel metal and the like. This treatment maybe efiected at temperatures of from about 40 to about 100 C., andpreferably at temperatures of from about -10 to about +50 C. Thepressure at which the reaction is carried out will vary with thereaction temperature used, the mol fractions of reactants and hydrogenfluoride catalyst present, and the volume of the particular reactorutilized. While many of the condensation reactions are carried out atsubstantially atmospheric pressure, it may be desirable in certaininstances and with certain reactants to carry out the reaction atpressures up to 100 atmospheres or more. It is convenient in mostinstances to operate the equipment utilized at the pressure generated bythe reaction mixture and the catalyst contained therein.

Hydrocarbons which may be .used as starting materials in the process ofthis invention include isoalkanes or isoparaflinic hydrocarbons, alkenesor olefinic hydrocarbons, alkynes or acetylenic hydrocarbons,alkadienes, aromatic hydrocarbons, hydrocarbons with condensed benzenerings, cyclanes or, cycloparaffinic hydrocarbons, and terpenes.

Typical utilizable alkanes include isobutane, Z-methyl butane,2,3-dimethylpropane, 2-methylpentane, 3-methylpentane,2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane,2,4-dimethylpentane, 2,2,3- trimethylbutane, 2-methylheptane,S-methylheptane, '4- methylheptane, 2,3:dimethylhexane,2,4-dimethy1hexane, 2,5-dimethylhexane, 2,2,3-trimethylpentane,2,2,4-trimethylpentane, 2,3,3-trimethylpentane, isononanes, isodecanes,isoundecanes, isododecanes, etc.

Suitable utilizable alkene hydrocarbons include eth- I ylene propylene,l-butene, 2-butene, isobutylene, pentenes, hexenes, heptenes, octenes,nonenes, decenes, undecenes, dodecenes, etc. High molecular weightpolyolefinic hydrocarbons such as those recovered from hydrogen fluoridecatalysts used to catalyze the polymerization of olefins, or to catalyzethe alkylation of isoparafiinic hydrocarbons with olefins, are alsoutilizable in the process of the present invention.

Utilizable alkyne hydrocarbons include acetylene, methylacetylene,ethylacetylene, propylacetylene, butylacetylene, etc.,dimethylacetylene, methylethylacetylene, diethylacetylene,ethylpropylacetylene, etc. These acetylenic hydrocarbons may alsocontain aryl and alkaryl substituents such as phenylacetylene,tolylacetylene, etc.

Suitable utilizable alkadiene hydrocarbons include propadiene orallene,derivatives of'allene, butadiene, 2- methylbutadiene or isoprene, etc.

Suitable utilizable aromatic hydrocarbons include benzene, toluene,o-xylene, m-xylene, p-xylene, ethylbenzene, 1,2,3-trimethylbenzene,1,2,4-trimethylbenzene, 1,3,5- trimethylbenzene or mesitylene,ortho-ethyltoluene, metaethyltoluene, p-ethyltoluene, n-propylbenzene,isopropylbenzene or cumene, etc. Higher molecular Weight alkylaromatichydrocarbons are also suitable such as those produced by the alkylationof aromatic hydrocarbons with olefinic polymers. Such products arereferred to in the art as alkylate, and include hexylbenzene,hexyltoluene, nonylbenzene, nonyltoluene, dodecylbenzene,dodecyltoluene, etc. Very often alkylate is obtained as a high boilingfraction in which case the alkyl group attached to the aromatichydrocarbon varies in size from C9 to C18.

Other suitable utilizable aromatic hydrocarbons include those containingan unsaturated side chain such as styrene, vinyltoluene, etc.

Other suitable utilizable aromatic hydrocarbons include those with twoor more aryl groups such as diphenyl, diphenylmethane, triphenyhnethane,fluorene, stilbene, etc. Examples of suitable utilizable hydrocarbonswhich contain condensed benzene rings include naphthalene, anthracene,phenanthrene, naphthacene, rubrene, etc. 7

Suitable utilizable cycloalkane hydrocarbons include allcylcycloalkanessuch as methylcyclopropane, methylcyclobutane, methylcyclopentane, m e th y 1 cy c l o hexane, etc,, aryl substituted cycloalkanes, such asphenylcyclopentane, phenylcyclohexane, etc. Derivatives of cycloalkanesformed by the loss of one molecule of hydrogen to produce cycloalkenesor cycloalkanes containing an unsaturated side chain are also Within thescope of the present invention, as are diolefiniccycloalkanes such ascyclopentadiene, etc. 7

Suitable utilizable' terpenic-hydrocarbons include menthane, limonene,thujane, earane, pinane, eamphane, sabinene, carene, alpha-pinene,beta-pinene, etc.

Carbohydrates which are condensed with hydrocarbons in the process ofthe presentinvention include simple sugars, their desoxy andomega-earboxy derivatives, compound sugars or oligosaccharides, andpolysaccharides. Simple sugars include dioses, trioses, tetroses,pentoses,

hexoses, heptoses, octoses, nonoses, and decose's. Compound sugarsinclude disaccharides, trisaccharides, and tetrasaccharides.Polysaccharides include polysaccharides composed of only one type ofsugar residue, polysaccharides composed of more than one type of sugarunit, polysaccharides composed of one-type of uronic acid unit, i.'e.,polyuronides, polysaccharides comprised of aldose (pentose or hexose)and uronic acid units, polysaccharides containing hexose unitsesterified with an inorganic acid, and polysaccharides containing aminosugar 1 units.

derivatives of simple sugars are formed by the replacement of a hydroxylsubstituent in a sugar with hydrogen thereby forming a methylor'methylene linkage. The

, desoxypentoses and desoxyhexoses are the most commonly occurring ofsuch compounds. The omega-carboxy derivatives of simple sugars, whichare suitable in the process of the present invention include tartronicaldehyde or its tautomer, hydroxypyruvic acid, org-dihydroxyacetoaceticacid, threuronic acid, 4-keto-2,3,5- trihydroxypentanoic acid, xyluronicacid, S-keto-hexanoic acids such as S-keto-allonic acid, S-keto-gluconicacid, 5-

.ketomannonic acid, S-ketogulonic acid, and S-keto-gallactonic acid,uronic acids such as glucouronic acid, mannuronic acid and gallacturonieacid, and the 6-ketoheptanoic acids. The simple sugars and theiromegacarboxy derivatives, as starting materials for the process of thisinvention, may be represented by the following general formula:

in which A=H and CHzOH, 11:: an integer from 1 to about 12 or so, andB=H, CHzOH, and COOH. As an example of the utility of this generalformula when A=H, n=1, and B=H, the compound is glycolaldehyde; whenA=H, 11:1, and B=CH2OH, the compound is glyceraldehyde; when A=H, n:l,and B==COOH, the compound is tartaronic semialdehyde, a tautomer ofhydroxypyruvic acid; when A=CH2OH, n=1, and B==H, the compound iss-dihydroxyacetone; when A=CH2OH, 21:1, and B==CI-I2OH, the compound iserythrulose; when A CHzOH, n=1, and B=COOH, the compound is or,'y-dihydroxyacetoacetic acid; when A=H, n=2, and B=CH2OH, the compoundis erythrose, or threose; when A=H, n=2, and B=COOH, the compound isthreuronic acid; when A=CH2OH, 11:2, and B=CH2OH, the compound isriboketose, or xyloketose; when A=CH2OH, n=2, and B=COOH, the compoundis 4-keto-2,3,5- trihydroxypentanoic acid; when A=H, n=3, and B=CHzOI-I,the compound is ribose, arabinose, xylose,

fucose (a desoxy semitugosan, the hexosans, such as starch, cellulose,

or lyxose; when A:H, '11::3, and B=-'COOH, the compound is xyluronieacid; when A=CH2OH, 11:3, and BzCHsOI-L the compound is psicose,fructose, sorbose, or tagatose; when A=CH2OH, 11:3, and B=COOH, thecompound is S-ketohexanoic acid; when A=H, n=4, and

B :CI-lzOH, the compound is allose, altrose, glucose, mannose, gulose,idose, gallactose, or 'talose; when A=H, 11:4, and B.=COOH, the compoundis a uronic acid; when A=CH2OH, n=4, and B '-CHzOH, the compounds areheptoses;'and when A=CH2OH, n=4., and BISQUE, the compounds are6-ketoheptanoic acids.

Theutilizable .oligosaccharides or compound sugars in eludedisaecharides such as the pentose-hexose saccharides includingglucoapiose, vicianose, and primeverose; the methylpentosc-hexosesaccharides including glycorhamnoside, and rutinose; and the dihexosessuch as turanose, maltose, lactose, cellobiose, gentiobiose, meliboise,sucrose, and trehalose. Other compound sugars arerepresented bytrisaccharides such as the'methylpentosef hexe'se saccharides includingrhamninose, and robinose;

the trihexose saccharides such as mannotriose; and the tri- .hcxosesincluding rafiinose, melezitose, and gentianose.

An example of a suitable tetrasaccharide is stachyose.

' Various polysaccharides are also utilizable in the proc-.

ess of the present invention. These polysaccharides in- I eludepentosans such as araban, methylpentosans such as inulin, mannan,galaetan, lichenin, levan, dextran, .and laminarin. ,All of. the abovepolysaccharides are com posed of one type of sugar residue. Otherpolysaccharides which are composed of more than one type of sugar unitsuch as the pentosans, like araboxylan and the hexosans likegalactornannan may be used. Other utilizable polysaccharides arerepresented by those composed of uronic acid units such as pectic acidand alginic acid; those composed-ofaldose (pentose or hexose) and uronicacid units such as gum arable, damson gum, gum tragacanth, linseedmucilage, pectins, and those containing hexose units este'rified with aninorganic acid such as certain seaweed polysaccharides like agar.

The hydrogen fluoride catalyst which is used in this process may be usedin anhydrous form or diluted with water to make a hydrofluoric acid ofthe desired concentration. The hydrofluoric acid may also be furtherdiluted with various inert diluents when it is desirable to operate theprocess of this invention with low hydrogen fluoride concentrations.Suitable inert diluents include normal paraffinic hydrocarbons such aspropane, n-butane, n-pentane, n-hexane, etc., and perfluoro derivativesof n-paraflinic hydrocarbons such as perfluoropropane,perfiuoro-n-butane, perfiuoro-n-pentane, perfiuoro-n-hexane, etc. Othersuitable diluents in these classes are apparent to one skilled in theart. For example, cycloparafiins as cyclopentane and cyclohexane may beused. In some instances, hydrofluoric acid of from about to about HPconcentration is desirable, and in some other instances it is mostdesirable to use anhydrous hydrogen fluoride as the catalyst.

This process may be carried out by slowly adding a hydrogen fluoridecatalyst to a stirred mixture of the hydrocarbon and carbohydrate orrelated material being subjected to reaction while maintaining thereaction temperature at from about -40 to about 100 C. By suitablecooling and/or heating means it is often advisable or desirable tocommingle the reactants and catalyst at a relatively low temperaturesuch as from about 80 to about -30 C. and then to permit the reactionmixture to warm gradually while the reactants and catalyst are stirredby suitable means such as a motor driven stirrer or other adequatemixing equipment. After the reaction has reached the desired degree ofcompletion, the hydrogen fluoride catalyst is removed from the reactionmixture by distillation at atmospheric or lower pressures or by passingan inert gas through the reaction mixture while maintaining it atrelatively low temperature. Also the entire glycogen,

reaction mixture and catalyst may be mixed with water ormay be added toice in order to quench the activity of the hydrogen fluoride catalystand permit separation of the organic reaction products and unreactedstarting materials from the catalyst. The organic reaction products mayalso be separated from aqueous hydrogen fluoride by means of an-organicsolvent such as ether in which some of the organic material may bedissolved. Further methods of isolating the reaction products areillustrated in the examples. Thus the product formed by reacting toluenewith glucose or cellulose in the presence of substantially anhydroushydrogen fluoride at 30 C. is separated "into an ether soluble and waterinsoluble product and an ether insoluble and water-soluble product.

The process of this invention broadly emphasizes the reaction ofcarbohydrates including simple sugars, their derivatives, compoundsugars, and polysaccharides with hydrocarbons such as isoparaflins,olefins, aromatics, naphthenes, and terpenes using as a catalyst,hydrogen fluoride.

The type of product is markedly affected by the length of time that thereactants are in contact with the hydrogen fluoride catalyst as well asthe temperature of reaction. This time factor will be set forth morefully hereinafter in the examples.

The reaction products of this process lead to materials havingdiversified uses. Some of these are enumerated as follows:

(a) Detergents.

(1) Szzlfonate type.Sulfonation of some of the products lead tocompounds of the R4O3H type which can be converted into surface activesalts.

(2) Sulfate type.Sulfation of these products lead to compounds of theROSO3H type which, if desired, can be converted into salts.

(3) Nom'onic type.The monohydrocarbon substituted products are watersoluble to diflerent degrees depending upon the size and nature of thehydrocarbon substituent. Thus, for example, it is possible to make aseries of surface-active agents with increasing hydrophobic-hydrophilicratio in the (d) Fermentation-Theconversion of many of th'ereactionproducts into other useful chemicals such as plastics, etc. canbeaccomplished by employing the products as a substratum for growingcertain species of bacteria. It has been observed that waterconcentrations of some of these products support the. growth of fungi.

(e) Pharmaceuticals.-Since many of the products which can be prepared bythe present process areeither completely new in constitution, orhitherto unavailable in appreciable amounts and combine the chemistry ofcarbohydrates on one hand, and of the hydrocarbons on the other hand,they open up acompletely new field of substances adaptable for use inmedicinal chemistry or in general chemical synthesis.

(1) Gellz'ng agenzs.-Various reaction products. are effective forgelling paraflinic or aromatic hydrocarbons. Thus, for example, smallquantitiesofone of thereaction products of toluene and fructose gelsbenzene, and pentane to a lesser extent.

The nature of this invention is illustrated further by the followingexamples which, however, should not be misconstrued to limit unduly thegenerally broad scope of the invention.

EXAMPLE I This example illustrates the reaction of toluene withcellulose. Cellulose is a polysaccharide containing glucoside linkages,and with all but oneof the potential aldehyde groups of the glucoseresidues involved in these glucoside linkages. This reaction was studiedat three temperatures, -30 0, 0 C., and +30 C., using a relatively largeamount of hydrogen fluoride and a toluene-cellulose mol ratio of greaterthan 2. At 0 C. the reaction was studied further by determining theeffect on the reaction of reducing the amount of hydrogen fluoridecatalyst. The type of product obtained by using approximately equal molsof toluene in cellulose in the reaction at 0 C. Was also studied. Theconditions for the reaction and quantities of materials used in each,are summarized in the following table:

ence of hydrogen fluoride Run No 1 2 3 4 5 6 7 8 9 10 Conditions ofReaction:

emp C -30 -30 0 0 0 0 0 0 "+30 +30 3 5 3 2 2 5 5 5 18, 4

Cellulose, gms 81 41 41 41 41 41 42 63 81 81 Toluene, gms 130 130 130217 260 217 21 33. 130 130 Hydrogen fluoride, gms. 204 222 236 114 41111 221 219 218 188 n-Pentane 0 O 0 0 0 62- 0 0 0 M01 Ratio,toluene/cellulose 1 2. 82 5. 73 5. 73 9. 43 11.32 9. 43 0. 88 0. 92 2.822. 82

1 Calculated as CoHmO ,m0lecr1lar weight 162.

molecule by reacting glucose with monoalkylbenzenes, in which the alkylgroup varies from C to C20.

(4) Detergent aids.-The structure of some of the products are related tocompounds found useful as detergent aids (that is, compounds which whenadded to a detergent in small concentrations rather markedly increasetheir effectiveness). They may accordingly find use in that field.

(b) Surface coatings and resinnqsome of thereaction products can be usedper se as surface coating materials. Resins can be made by heating manyof the reaction products with formaldehyde, urea, phenol, aniline, etc.,and combinations of the above-enumerated compounds.

(c) Explosives-Nitration of many of the reaction products will giveexplosives. These explosives will contain in some instances nitro groupsattached to aromatic .rings as well as being nitro-alcohol derivatives.

The above experiments were all conducted in substantially the samemanner except for minor changes in re covery techniques.

As an example of the manner of conducting these experiments, thefollowing detailed description of run 10 is given: Into a 1 liter steelturbomixer autoclave was sealed 81 grams of cellulose and grams oftoluene. With stirring, the autoclave was cooled to -50 C. and 188 gramsof hydrogen fluoride added. The temperature was allowed to rise to 30 C.during two hours and the stirring continued for an additional 2 hoursat30-35 C. Then a stream of nitrogen was passed through the reactor atatmospheric temperature for 16 hours; 13 cubic feet of nitrogen wereused. The hydrogen fluoride and toluene volatilized were condensed at 78C., their recovery being: hydrogen fluoride, grams; and toluene, 36grams. A substantial amount of hydrogen fluoride remained behind in thereaction mixture althoughmost. of

it could have been recovered by prolonging the nitrogen purge. Theautoclave was opened and the product found to be a heavy fuming liquid.Water was added to extract the remaining hydrogen fluoride. This aqueouspart was neutralized with magnesium oxide and concentrated to yield awater-soluble product. The water-soluble part was dissolved in benzene,the benzene solution filtered, and the benzene removed by evaporation.This product was a brown solid and weighed 146 grams. It was separatedinto an ether soluble and ether insoluble portion. The ether solublepart was soluble in benzene and acetone but insoluble in water. Theether insoluble part was soluble in acetone, and in hot water from whichit could be recrystallized.

Several conclusions have been drawn from the reactions as outlined inthe above Table I. There was no indica tion that toluene reacted withcellulose in the presence of hydrogen fluoride at -30 C. The two lowtempera ture experiments, runs 1 and 2, were similar except for the timeof contacting. The results obtained indicated that the cellulose slowlylost its form and became an insoluble gray powder, the carbon-hydrogencontent of which approximated cellulose. This gray powder may representa shorter polymer system than the initial cellulose. Thus treatment ofpolysaccharides alone with a hydrogen fluoride catalyst results ininteresting new compositions. An elementary analysis of the gray powderis: percent carbon, calculated for CsHioOs, 44.4%; found, 41.66%;percent hydrogen calculated for CsH1005, 6.2%; found, 6.52%. Thus 30 C.is too low a temperature to involve toluene in reaction with cellulosealthough cellulose itself is changed.

Runs 3, 4, 5, 6, 7, and 8 were conducted at C. It was established thatthere is a critical amount of hydrogen fluoride catalyst necessary tocause reaction and that below that amount (which was not accuratelyestablished) there is no involvement of toluene in the reaction withcellulose (run In run 5, after the autoclave was opened the toluenelayer was decanted ed and evaporated to dryness leaving a residue ofonly 0.3 gram. After the residual hydrogen fluoride was removed from theresidue over steam, 41 grams of product was obtained. Of this 41 grams,3 grams was soluble in hot water and the solution contained a reducingsugar as indicated by a Fehlings solution test. The insoluble residuewas assumed to be cellulose or partially hydrolyzed molecules thereof.

Where the requisite amount of hydrogen fluoride is present, cellulosereacts with a molar excess of toluene at 0 C. in a reaction whichprobably goes via several different paths. In run 3, 41 grams ofcellulose gave more than 33 grams of a pure material which was shown tobe l,l-di-p-tolyl-l-desoxy'D-glucitol, the structural formula of whichmay be represented as follows:

. solid material after several crystallizations from alcohol hada'melting point of 160l61 C., is soluble to the extent of about 1% inWater at 100 C., about 1.5%

in ethanol at C., and can be recrystallized from benzene. The presenceof 5 hydroxyl groups in the compound was shown by the formation of itspentaacetate derivative. The elementary analysis of the petaacetatederivative corresponded very closely to that calculated for CaoHasOm.The compound was also oxidized by chromic acid to4,4-di-carboxybenzophenone, the dimethyl ester of which was identifiedby its melting point of 224 C. The observed yield of1,l-di-p-tolyl-l-desoxy-D-glucitol can undoubtedly be markedly increasedby a more refined method of working up the remainder of the product. Itis noteworthy that so much pure compound survives in the strong hydrogenfluoride environment. This same roduct was isolated in run 4, and run 6.

From the structure of the 1,1-di-p-tolyl-l-desoxy-D- glucitol, it can beseen that its formation required two mols of toluene for each glucoseunit in the cellulose. Experiments were carried out (runs 7 and 8) todetermine the product resulting from reacting approximately equalmolecular amounts of toluene and cellulose, based on the glucose unitsin cellulose. It was expected that a mono-tolylglucitol would result.When the experiments were made, the product was very water soluble incontrast to the moderately water soluble ditolylglucitol. All attemptsto isolate a pure product failed; the product, however, did not reduceFehlings solution and the absence of any glucose was thus proven. When awater solution of the product was concentrated to a syrup, smallcrystals appeared, but the attempts to isolate them were not successful.

Experiments were also conducted at C., runs 9 and 10 and the dataavailable, although incomplete, gives an indication of the type ofreaction which occurs. The 30 reaction product from these runs consistsof two parts, an ether soluble-water insoluble part and an etherinsoluble-water soluble part. The ether soluble-part insoluble part is alight brown material which gives a resinous surface when plated out froma benzene solution. A portion of this other soluble-water insoluble partwas sulfonated by cold concentrated sulfuric acid to give a watersoluble material with surface-active properties. The water soluble partof the product imparted a marked tendency of foaming to its solutions. Apure compound melting at 214-216 C. was isolated. This compound issomewhat soluble in hot water, but when the water solutions were cooledthey gelled. The completely dried substance was very hygroscopic. Itselementary analysis indicated exactly the empirical formula CrsHnaOs.

EXAMPLE II The condensation products of carbohydrates and hydrocarbonsas shown in Example I, cellulose and toluene, constitute a new sourcefor certain polyhydroxy compounds. One use of such compounds is toesterify them with nitric acids to give nitrates similar tonitrocellulose. Pure 1,l-di-p-tolyl-l-desoxy-D-glucitol from thereaction of toluene with cellulose at 0 C. was available and accuratelyserved as a convenient intermediate on which to work. The experimentalprocedure followed in the nitration was exactly the same as that givenfor the preparation of pyrocellulose in the chemical literature. Equalvolumes of 96% sulfuric acid and nitric acid were mixed together.' ml.of this nitrating mixture was poured into a breaker containing 2.5 gramsof 1,1-di-ptolyl-l-desoxy-D-glucitol produced in run 3, Example I.Immediate reaction evolved heat and nitric oxide fumes. The mixture wasstirred occasionally over a period of 30 minutes after which time thesyrupy red product was transferred to cold water wherein it changed to ayellow solid. The solid was filtered off and purified subse- In ExampleI, all of the experiments were conducted with cellulose as a reactantand some of the products formed were characterized by the presence of aglucose unit in their structure. To demonstrate the probableinterchangeability of cellulose and glucose, an experiment similar toExample I, run 3, was made with glucose. The procedure utilized wassimilar to that described in Experiment I.

In a one liter nickel-lined steel turbomixer autoclave was sealed 45grams of glucose and 69 grams of toluene. After sealing, the autoclavewas cooled to about 50 C., and 211 grams of hydrogen fluoride was added.The autoclave was maintained at C. for three hours with stirring andthen the contacting continued for an additional two hours while a streamof nitrogen was passed therethrough in order to volatilize most of thehydrogen fluoride. The autoclave was opened and the contents found toweigh 118 grams. The liner was placed overnight in a hood-draft and lost24 grams to a final net weight of 94 grams, essentiallyhydrogen-fluoride free. The product was broken down into the followingportions: 25' grams which was completely water insoluble; 22 grams whichwas insoluble in cold water and partially soluble in hot water; and 43grams which was water soluble. The portion of the product insoluble incold water and partially soluble in hot water melted at 159-l61 C. andwas shown by crystalline form and mixed melting point to be identicalwith the previously identified sample of1,l-di-p-tolyl-l-desoxy-D-glucitol. The water soluble portion of theproduct also contained a substantial amount of the above compound,together with another component or components not identified. Thesolubility of the di-tolylglucitol in water is apparently increased bythe presence of the unknown, more soluble material. The more watersoluble product is possibly the monotolylglucitol.

Thus cellulose and glucose are probably interchangeable in the reactionwith toluene to give the same products but not necessarily withequivalent yields. For laboratory purposes glucose may be employed moreconveniently than cellulose because of the bulky nature of the latter.Furthermore, economic factors would lead one to the use of glucose, inthe form of corn syrup perhaps, as a more economical starting material.

EXAMPLE IV The preparation of 1,l-di-p-tolyl-l-desoxy-D-glucitol fromcellulose and toluene and from glucose and toluene has been described inExamples I and III, respectively. The present example gives data from anumber of preparations of that material carried out primarily to make alarge quantity for further laboratory work. In the course of thepreparative work, additional knowledge about increasing yields has beenobtained. It has been possible to obtain pure sharplymelting1,1-di-p-tolyl-ldesoxy-D-glucitol in yields up to about 70% based uponthe weight of the cellulose charged. There is an additional materialcontaining a substantial amount of the pure substance together withother reaction products in which glucose and toluene are respectivelyprobably combined in the ratio of 1:1, 2:2, and/or 3 or 4:2. Suchcompounds are alcohol soluble by virtue of'their relatively largerhydrophilic part of the molecule.

The procedure followed in-the first three experiments of this series issimilar to that described in Example I. In these experiments, thereactants were charged into a turbomixer (containing a1 liter nickelliner), stirred for the designated time at the temperature employed andfinally the contents of the reactor were flushed with nitrogen. Thetreatment of the products obtained varied somewhat in each case. Thefollowing table summarizes the data obtained:

Table II.Reacti0n of cellulose or glucose with toluene in the presenceof hydrogen fluoride The crude product from Run 11 was treated invarious ways in order to determine a possible method for obtaining1,l-di-p-tolyl-l-desoxy-D-glucitol in pure form. Recrystallization fromwater, alcohol, alcohol-water mixtures, chloroform, and acetone wasattempted. The best solvent for. this purpose was found to be water.

Virtually all of the crude product recovered from run 12 was soluble in750 m1. of boiling water. This was filtered and charcoal added. and thehot solution filtered again. The filtrate was evaporated, thenredissolved in 400 ml. of water. This solution was then made alkalinewith ammonium hydroxide. A brown amorphous precipitate which formed wasfiltered OE and the filtrateconcentrated. 45 grams of this dark brownmaterial was obtained.

From run 13, a 40 gram portion of the crude product was dissolved incold water and filtrated. A small quantity (1.8 grams) of dry crystalswas obtained. The filtrate was neutralized with 30 grams of potassiumcarbonate and evaporated over steam. By computing the portionofpotassium fluoride that should be present as a solid in the dryproduct, it is assumed that 39 grams of the desired product. Wasrecovered. The remainder of the product from this run was then treatedin this same manner.

In the following experiments, the reactants were charged into theturbomixer'containing a nickel liner as before. They were stirred forthe designated time at the temperature employed. The autoclave was thenremoved from the turbomixer and super-cooled ice added directly to theliner contents. The solid product which separated at this stage was thenfiltered off in a Biichner funnel. The filtrate was discarded. The wetcake from the Biichner tunnel was dried over steam and weighed The.dried cake was then treated in one of two ways: it was either hydrolyzedwith boiling water and then extracted with ether'or vice versa. Ineither case the dry material obtained was then dissolved in boilingwater and filtered. The filtrate was set aside to cool and the productcryst-aL lizedout on standing.v The product was then filtered off illand dried after which its melting point was determined. The followingtable summarizes the data obtained:

Table [IL-Reaction of cellulose with toluene in the presence of hydrogenfluoride Run No l4 16 17 18 10 20 Conditions of Reaction:

Temperature, "C 0 0 O 0 0 0 0 Contact Time, Hrs 3 3 3 5 l 3 2OReactants:

Hydrogen Fluoride, gins-.. 235 210 332 213 2L7 29,5 205 Toluene, gms.172 174 129 172 1.73 172 173 Cellulose, gms 81 41 41 41 50 50 Recovery:

Toluene, rnl 6 Trace Trace Trace Trace Cellulosic material, gins. 4 6 43.5 4 8 Dried Untreated Product, gm 60 72 77 83 60 88 113 Ether solublematerial, gms 22 19 t 22 60 Dry ether extracted product, gins" 58 57 454). Dry recrystallized product, gross..- l7 28 b 213 2() u 26 H 20 BEther extraction after hydrolysis.

b Ether extraction before hydrolysis.

The dry recrystallized product was pure 1,1-p-tolyl-ldesoxy-D-glucitol,melting point l57-l59 C. It should be observed that the contact timeeflects the yield of products. The water soluble product obtained,although not mentioned in the table, was investigated and will bedescribed hereinafter. it should be noted also that along contact timedecreases the yield of 1,1-di-p-tolyl-1-desoxy- D-glucitol and increasesthe yield of ether soluble material. A short contact time (1 hour)reduces the yield of the ether soluble material and also leaves a largeamount of toluene unreacted.

EXAMPLE V In Example II, the nitration of 1,1-di-p-tolyl-1-desoxy-D-glucitol was described. Further nitrations of this compound have beenconducted and are described as follows: 37.5 ml. of concentrated nitricacid was cooled to 0 C. by immersion of its container in an ice-saltbath. To this was then added 2.5 gms. of 1,1-di-p-tolyl-1-desoxy-D-glucitol. The mixture was stirred and maintained at 0 C. while 37.5ml. of concentrated sulfuric acid (28%) was added dropwise. Ayellow-orange product appeared in the reaction mixture. The reactionmixture was then poured over ice and the solid product which separatedwas filtered. This yellow-orange product was then boiled with water andfiltered, and this latter procedure repeated. On drying, 4.8 grams of anamorphous product was obtained.

2.5 grams of 1,l-di-p-tolyl-l-desoxy-D-glucitol was nitrated by addingthe compound to 37.5 ml. of concentrated acid cooled to 0 C. by means ofan ice-salt mixture. The nitric acid solution was then poured over ice.No product separated at this point so the solution was heated toboiling, filtered, and set aside to cool in a refrigerator. Aprecipitate was obtained with a melting point of -1 12 C. The nitrogencontent of the precipitate was 17.22%. This is an exceptionally highnitrogen content. To check the results obtained, a duplicate experimentwas made in which again, 2.5 grams of 1,1-di-p-tolyl-l-desoxy-D-glucitolwere added to 37.5 ml. of concentrated nitric acid cooled to 0 C. by anicesalt mixture. The nitric acid reaction mixture was removed from theice-salt bath and allowed to stand until the temperature reached 20 C.,at which time the mixture was poured over ice and yellow precipitateseparated. The nitrogen content of the product was 5.07%, the carboncontent 55.62%, and the hydrogen content 5.03%. This product was solublein ether, acetone, and chloroform, but insoluble in toluene. It may beassumed the high value of nitrogen reported in the first experiment wasdue to contamination of the product with nitric acid and/ or oxides ofnitrogen. The value of 5.07% for the nitrogen content of the productwould correspond to 1,1-di-p-tolyl-l-desoxy-D-glucitol with two of thehydroxyl groups of the carbohydrate chain esteri- EXAMPLE VI Two resinsof the alkyl type were produced from 1,1- di-p-tolyl-l-desoxy-D-glucitoland phthalic anhydride. In one case an excess of phthalic anhydride wasused; in the other case a deficiency. The experiments were conducted asfollows: 1 gram of 1,1-di-p-tolyl-1-desoxy- D-glucitol and 2.5 grams ofphthalic anhydride were placed in a flask. The mixture was heated forapproximately 20 minutes at 200250 C. The material was dissolved inacetone and the acetone then evaporated. The residue was then boiledwith water and the watersoluble resinous material filtered oflf. A browncolored brittle material was obtained.

in another experiment, 2 grams of l,l-di-p-tolyl-ldesoxy-D-glucitol wasplaced in a beaker with 1.2 grams of phthalic anhydride. The mixture washeated at approximately 200-250 C. for 20 minutes. A brown coloredbrittle material was obtained.

The two resins produced were similar in appearance; however, the oneproduced by using an excess of phthalic anhydride was more brittle.

EXAMPLE VII The reaction of toluene with glucose has been describedpreviously in Example III. In this example, a modified laboratoryprocedure for the preparation of 1,l-di-p-tolyl-l-desoxy-D-glucitol fromglucose is described. This modified procedure is based upon theinsolubility of lithium fluoride, which allows a neutralization of thehydrogen fluoride by lithium hydroxide after the reaction has beencompleted. Subsequent filtration removes lithium fluoride from the watersoluble organic products of the reaction.

An outline of the procedure used in reacting glucose or cellulose withtoluene and which is used in some of the experiments in the followingexamples, is as follows: into a one liter turbomixer was sealed 50 gramsof the carbohydrate (either glucose or cellulose) and a considerablemolar excess of toluene (172 grams). The autoclave was cooled to about50 C. and a charge of anhydrous hydrogen fluoride added (about 230grams). An ice bath was placed around the autoclave which was stirredfor a specified period of 0 C. Then,

' a rapid stream of nitrogen was passed through the reacton mixture forone to two hours while continuing to stir at 0 C. This removed most ofthe hydrogen fluoride and a large part of the toluene. After terminatingthe nitrogen stream, the autoclave was evacuated on a vacuum line forabout 5 minutes. The autoclave was then opened and the contentstansferred to a silver dish. This was allowed to stand in a. vigoroushood-draft for a number of hours. The product now contained only 1020grams of occluded hydrogen fluoride. It was next separated into twosegments, cold water soluble and insoluble, respectively. The watersolution was brought to a pH of 9 with a solution of lithium hydroxideof known concentration. The precipitate of lithium fluoride was filteredofl and the filtrate concentrated to dryness. The residue was treatedwith about 400 ml. of water and a second batch of lithium fluoridefiltered off. The filtrate was now essentially free of lithium salts andwas taken to dryness over a steam bath. Thereafter, the water solubleand insoluble portions of the product were investigated for the purposeof separating out pure chemicals therefrom.

In a cellulose-toluene reaction, 231 grams of hydrogen fluoride, 50grams of cellulose, and 172 grams of toluene were contacted for 3 hoursat C. in a turbomixer, after which time a rapid stream of nitrogen waspassed through the autoclave for one hour at 0 C. to sweep out most ofthe hydrogen fluoride. The autoclave was opened and the contents pouredinto a silver dish which stood in a hood-draft for 18 hours at roomtemperature. The net product at that point was 144 grams. The 144 gramswas washed twice with 400 ml. of cold water, then boiled for 20 minuteswith 600 ml. of water. After cooling, the solution was filtered and thesolid removed thereby was dried under a lamp. From this solid (64 grams)an ether soluble portion of the reaction product amounting to 24 gramswas extracted. The remainder of the solid product which was not solublein ether was crystallized from water in which it was sparingly solubleat the boiling point. 20 grams of 1,1- di-p-to-lyl-l-desoxy-D-glucitol(melting point 150-156 C.) was isolated. The water solutions from thefirst extraction of the crude solid product, including the filtrate fromthe filtration step, were neutralized with a solution of lithiumhydroxide. The precipitated lithium fluoride was filtered oif and thefiltrate taken to dryness over a steam bath. The residue was dissolvedin about 200 ml. of water, and a small quantity of additional lithiumfluoride filtered oif. The filtrate was then concentrated to yield aheavy syrup, weighing 34 grams.

was dried. The 67 grams'of dry solid was ether extracted and 15 gramsofether soluble products separated. The remainder was dissolved in 3%liters of boiling water. On cooling, 18.5 grams of1,1-di-p-tolyl-l-desoxy- D-glucitol was recovered; melting point 154-157C. The water solutions were neutralized with lithium hydroxide and afterremoval of the insoluble lithium fluoride, concentration of the watersolution yielded 23.6 grams of a heavy syrup.

EXAMPLE VIII In previous examples, the reaction of an aldose sugar witha hydrocarbon in the presence of hydrogen fluoride was described. Thisfollowing example contains a description of a rather intense study ofthe reaction of a ketose sugar, namely, fructose, with an aromatichydrocarbon, toluene, in the presence of hydrogen fluoride. The reactionwas studied mainly at 0 C. using contact times of from about 3 to about66 hours; one reaction was studied at 30 C.

An outline of the procedure used in reacting d-fructose with toluene inthe presence of hydrogen fluoride is as follows: d-fructose and toluenewere sealed into a 1 liter turbomixer. After cooling to about C.,hydrogen fluoride was pressured into the system from a weighed bomb andthe contactor stirred for the required time at ice temperature (in onecase at 30 C.). A stream of nitrogen was then passed through the reactorfor 1-3 hours; this removed most of the hydrogen fluoride. The autoclavewas opened and the contents transferred to a silver dish which wassubsequently placed in a hood-draft for 18-24 hours. The hydrogenfluoride still remaining in the product was only about 20 grams at thispoint. Then the product was washed thoroughly with pentane to remove anypentane-soluble component, after which it was separated into a coldwater soluble and cold water insoluble fraction. Each of these portionswas then separately worked up to separate pure compounds therefrom.

presence of hydrogen fluoride Charge (17):

d-Fructose Toluene HF Run N0 21 22 23 24 25 26 27 Conditions ofReaction:

Temp, 0 0 0 0 0 0 30 Contact Time, Hrs 3 5 16.7 20 66 3 Recovery, Gms;

Pentane-Soluble.-. 2 2 1 10 24 Water-Soluble 42 5O 39 35 15 10 1. 3Water-Insoluble a... 7 15 35 48 84 130 84 Net Total 49 67 76 84 99 159109. 3

Toluene Reacted, Grns., 0 17 26 34 49 91 59 Percent of Water-SolubleMaterial,

Also Acetone-Soluble 44 56 83 97 100 100 Acetone-Soluble, Gms 18 28 3234 15 10 0.6 Yield of OnHmOt, Gms. 9 14 20 19 2 0 Yield Of ClB 2203, Gms5 ll 16 28 46 Percent of 020112403, in Water-Soluble Fraction 39 31 3733 0 h Exclusive of pentane-soluble. b In run 26 the charge was:d-i'ructose, 75 grams; toluene, 215 grams; HF, 336 grams.

Glucose and toluene were, reacted for 3 hours at 0 C. in a procedureidentical with the cellulose experiment described above. In thisexperiment, the reactants were 234 grams of hydrogen fluoride, 50 gramsof glucose, and 172 grams of toluene. The product obtained when removedto a silver dish, weighed 119 grams. The 119 grams were transferred to atwo liter beaker and thoroughly mixed with 500 ml. of cold water. Theinsoluble part was a yellow fluid mass. The water was decanted'off andthe insoluble part heated for 20 minutes with 700 ml. of boiling water.After cooling, the insoluble product, now a gray annular solid (67grams) In the previous examples relating to the glucoseandcellulose-toluene reactions, it was shown that at 0 C. and 3hourscontacting time, suificient reaction occurred to involve about twomolecules of toluene with a glucose residue and an important product ofthe reaction was 1,l-di-p-tolyl-l-desoxy-D-glucitol. In working withfructose at 0 C. it was observed that a much slower reaction took place.Three hours of contacting at 0 C. resulted in only a negligible amountof reaction of toluene with fructose. As the contact time was increased,the amountof toluene reacted, rose rapidly. The data show that thewater-soluble portion first increases rapidly with CHsOH t i-ons nohnHCIJOH n on The water-insoluble portion of the reaction productscontained another compound which could be isolated by extraction andcrystallization with n-propyl alcohol, by which method it was recoveredin quantities amounting to about 30% of the insoluble fraction. Thissubstance melts at 210 C. and corresponds to the empirical. formula forCzoHziOs. This compound could not be fixed in molecular weight becauseit always associated with itself or with the solvent employed. Chromicacid oxidation of the compound yielded 4,4-dicarboxybenzophenone. Theexact structure of this compound has not been determined. It has a veryuseful characteristic, however, in that it forms firm gels with benzeneand other hydrocarbons. When benzene is heated to the boiling point withabout of this compound, the cooled solution sets to a stiff gel. It hasalso been observed to gel pentane, cyclohexane, and several otherhydrocarbons.

Components of higher complexity than the two pure compounds isolated,are high in amount in the product. Chromic acid oxidation of thewater-insoluble part of the product which had been depleted of itscontent of the pure compound melting at 210 C., gave both terephthalicacid, and 4,4'-dicarboxybenzophenone. This indicates a carbohydratechain in which one of its carbon atoms is attached to two tolyl groupsand an additional carbon atom (or more) attached to a single tolylgroup.

Run 26 in Table IV employed a higher concentration of reactants than theother runs. A very long contact time (66 hours) was used and this wasfound to enhance still further the conversion of fructose into the purecompound melting at 210 C. The conversion of 75 grams of fructose gave46 grams of this compound.

Run 27 in Table IV employed 30 C. for the reaction. The course of thereaction here was markedly dilierent. More toluene reacted in threehours at 30 than in 45 hours at 0 C. While the investigation was notintensive, no successful isolation of any pure compound from the productwhich was nearly all water-insoluble resulted. A noteworthy distinctionfrom the product at 0 C. was the large fraction of pentane-solubleproduct found.

EXAMPLE IX l-sorbose was reacted with toluene in the presence ofhydrogen fluoride in a manner similar to that described in Examples VIIand VIII. The following reactants were charged to a 1100 milliliterturbomixer autoclave: 50 grams of l-sorbose, 172 grams of toluene, and234 grams of HP. The mixture was contacted for 45 hours at 0 C. andatmospheric pressure. Most of the hydrogen fluoride was flushed from thesystem by passing a stream of nitrogen through the autoclave. Thereaction product, when practically free of hydrogen fluoride, weighed126 grams. From this 126 grams was obtained 82.5 grams of a toluenefree,HF-free product. This product was separated into 7 grams ofpentane-soluble material, 14 grams of watersoluble material, and 61.5grams of water-insoluble product, 18.5 grams of a pure material meltingat 215 C. was obtained. Chromic acid oxidation of a portion of this purematerial yielded 4,4'-dicarboxybenzophenone identified by a methyl estermelting at ZZZ-224 C. Equal parts of the sorbose product melting at 215C. and the fructose-toluene product melting at 209-210 C. (Example VIII)gave a mixed melting point of 204-206 C. and the compounds are,therefore, assumed not to be iden' tical. This sorbose-toluene reactionproduct formed a clear stable gel with benzene when added thereto inabout 5% by weight.

EXAMPLE X This example relates to the preparation of l-p-tolyl-l-(4-methylcycl0hexyl)-1-desoxy"D-glucitol by the catalytic hydrogenationof 1,1-di-p-tolyl-l-desoxy-D-glucitol in the presence of a platinumcatalyst and in the presence of nickel-kieselguhr.

In one experiment, 0.4996 gram of 1,1-di-p-tolyl-l-desoxy-D-glucitolwere charged to a hydrogenation appatus along with 0.0558 gram ofplatinum catalyst, 10 cc. of tetrahydrofuran and 0.5 cc. of acetic acid.These materials were kept under atmospheric hydrogen pressure for 168hours. At the end of this time, sufficient hydrogen had been absorbed togive a calculated hydrogen number of 191.5 compared with a theoreticalvalue of 6. Under similar conditions, ordinary aromatic compoundshydrogenate easily and rapidly to saturation. It is apparent thatl,l-di-p-tolyl-l-desoxy-D-glucitol accepts hydrogen with difiiculty.

In another experiment, 10 grams of 1,1-di-p-tolyl-l-desoxy-D-glucitolwere dissolved in 150 ml. of ethyl alcohol placed in a high pressurerotating autoclave along with 5 grams of nickel-kieselguhr catalyst.atmospheres of hydrogen was then pressured into the autoclave, afterwhich the autoclave was heated to C. for 2 hours. On cooling, it wasnoted that 13 atmospheres of hydrogen had been absorbed, which on thebasis of the size of the autoclave used, gave a calculated hydrogennumber of 5.4. The product was obviously a mixture of differentcompounds, but one pure compound melting sharply at -141 C. wasisolated. This pure compound corresponds to the formula C20H3205.H20,which would correspond to the hydrogenation of one of the two tolylrings. The elementary analysis is C20Ha205.H2O is: carbon: 65.70% found,and 64.84% calculated; hydrogen: 9.25% found, and 9.32% calculated.

In the next experiment, 15 grams of 1,1-di-p-tolyl-1-desoxy-D-glucitolwas placed in a high pressure rotating autoclave along with ml. of 95%ethanol and 5 grams of nickel-kieselguhr catalyst. The autoclave wascharged to 100 atmospheres with hydrogen and heated as high as 150 C.during a six-hour period. The calculated hydrogen number here was 5.6.The final gas in the system was not analyzed, but it is believed thatsome decomposition occurs at 150 C., and therefore, the values forhydrogen consumption are not trustworthy. Although the product obtainedwas complex, the same product as separated heretofore corresponding toC2oH32O5.H2O was obtained. The elementary analysis found for the productwas close to the theoretical value.

In another similar experiment with nickel catalyst in a high pressureautoclave, it was observed that heating for two hours at 100 C., did notbring about more hydrogen absorption. A total product from thisexperiment was obtained in a crystalline form; its melting point of92-120 C. showed it to be a mixture of at least two compounds. From thisreaction product, a pure compound melting at 140141 was isolated andwhich elementary analysis corresponded to C20H3205. A mixed meltingpoint as well as elementary analysis showed this to be different fromthe similarly melting product described in the previous experiments.

1 7' EXAMPLE x1 In this example, 50 grams of glucose was sealed in an850 cc. rotating autoclave, to which was added 64 grams of isobutane and139 grams of hydrogen fluoride after cooling. The autoclave was thenallowed to warm to room temperature and the reactants were kept incontact for 1534 hours (64 days) during which time the autoclave wasrotated 23% of the time. The reaction product was then isolated byreleasing the pressure in the system through a line from the top of theautoclave, followed by purging of the autoclave with nitrogen, thenremoving the remaining materials. The hydrogen fluoride and unreactedisobutane were condensed and the amounts recovered determined. 48 gramsof condensable gas consisting essentially of isobutane was recovered. Asolid product was obtained weighing 50 grams and which was hydrogenfluoride free.

The product was separated into three portions as follows:

(A) This portion, weighing two grams, was soluble in water and did notreduce Fehlings solution.

(B) This portion, weighing 14 grams was soluble in benzene, n-propylalcohol, and ethyl alcohol, and slightly soluble in boiling pentane. Itwas a dark red viscous oil, fluorine-free, and whose elementary analysisis given in the following table:

(C) A portion, weighing 34 grams, was obtained, and which was insolublein water and benzene and about 8% soluble in pyridine. By elementaryanalysis it was found to contain 67.92% carbon, 7.14% hydrogen, and2.96% ash.

From the amount of isobutane recovered, it was calculated that theisobutane entering the reaction was approximately molecularly equal tothe glucose in the system. The benzene-soluble yield, a viscous materialanalyzing C10H1605 (empirical formula), indicates one butane unit andone glucose unit minus some hydrogen. It is not suggested that thissegment actually is an individual; it is undoubtedly complex in nature.The conclusion was, however, that isobutane must have entered into thereaction because this material is 63% carbon and hydrogen as compared toonly 47% carbon and hydrogen in the starting glucose. The insoluble partof the product had an even greater carbon and hydrogen content, 75%;however, it is somewhat contaminated with inorganic materials.

By analogy with the products obtained by the hydrogen fluoride catalyzedreaction of cellulose or glucose with toluene, as described in previousexamples, it might be expected that the isobutane would attach itself tothe aldehyde carbon atom and give a product of the following structure:

hydration to an olefin-acting substance which could alkylate isobutanein the center part of the sugar chain. It is unexpected that anhydroushydrogen fluoride will catalyze the condensation of a carbohydrate suchas glucose with an isoparaflinic hydrocarbon such as isobutane. Theexpected conversion would necessarily entail an extensive dehydration ofthe carbohydrate because of the strong dehydrating action of anhydroushydrogen fluoride and of hydrofluoric acid of from about to about HFconcentration.

EXAMPLE x11 This example describes a study of the reaction of cellulose,a polysaccharide, with dodecylbenzene in the presence of hydrogenfluoride. The reaction was studied mainly at 0 C. using contact times offrom about 3 to about 70 hours; one reaction was studied at about 30 C.

The experimental procedure followed the outline given in Example VHI forthe reaction of d-fructose with toluone. The following table lists theexperiments carried out, the conditions used, and the reaction productsob tained:

Table V.Reaction of cellulose with dodecylbenzene iii the presence ofhydrogen fluoride Run N o 28 29 3O 31 32 33 Charge Gms.: Cellulose 30 a041 61 61 so Dodecy1benzene 100 100 172 176 258 260 Hydrogen Fluoride 228227 232 236 238 239 Conditions: 1 Temp. O 0 0 0 0 0 34 Contact Time, Hrs3 5. 5 21 44 70 16 Recovery, Gms.:

Water-Soluble 25 39 54 Water-Insoluble 160 160 260 Dodecylbenzene 83 91149 234 152 B.P. Dodecylbenzene. Trace 5 20 10 26 122 B Water-solublematerial low and not determined. This run in addi- The dodecylbenzeneused in the above experiments was a fraction boiling at 290 C. from themajor plateau in the C18 range of a product from the alkylation ofbenzene with propylene tetrarner. This material was completelyresistantto oxidation by chromic acid or alkaline potassium permanganatesolutions, indicating that the alpha carbon atom attached to thearomatic nucleus had 3 other substituent groups. All of the work wascarried out at a reaction temperature of 0 C. except one run at 34 C. Itwas noted that when the first experiment (run 28) was completed, thatdodecylbenzene is far less reactive than toluene since no reaction wasobserved during three hours of contacting at 0 C. When the contactingtime was extended to 5.5 hours (run 29), 5 grams of a higher boilingsegment, believed to be the reaction product, was isolated. This segmentwas not identified further.

In the next experiment, run 30, the contacting was continued for 21hours. From this reaction, grams of an ether-soluble-water-insolublesegment was obtained, along with 40 grams of awater-soluble-ether-insoluble material. The 160 gram fraction wasseparated by ordinary distillation followed by steam distillation and140 grams of dodecylbenzene was recovered along with 20 grams of ahigher boiling product. This 20 grams was dissolved in pentane and uponevaporation yielded a brown material of a buttery consistency,resembling a fiber grease. This material was surface-active as evidencedby its imparting a soapy feeling when washed with. Elementary analysisfor carbon and hydrogen are as follows. carbon: 80.12% found, and 77.01%calculated for C42H7005; hydrogen: 10.73% found, and 10.77% calculatedfor C42H70O5. This elementary au- HCOH HO( 3H HCOH HCOH

CHzOH This product was tested as an additive for a lube oil forenhancing its viscosity index. The viscosity index for the base stock (aPennsylvania lube oil) was 102.7; with 5.1% of the product dissolvedtherein, its viscosity index was raised to 113.1. Theether-insoluble-water-soluble portion of the product (40 grams) wasdissolved in water and evaporated to dryness. During this evaporationsome hydrogen fluoride was evolved. 25 grams of a dry brown powder wasobtained; its elementary analysis found was: carbon, 39.22%; hydrogen,6.05%.

While reaction times of at least five hours at C. were necessary to getappreciable reaction of dodecylbenzene with cellulose, there was, on theother hand, little improvement in yields at reaction times above 20hours. This would indicate that the dodecylbenzene used became depletedof a reactive isomer, leaving a refractory material. This conclusion isborne out by the data of run 31, Table V. In run 31 the dodecylbenzenecharged was recycle material from previous runs and it will be observedthat the product (boiling point greater than dodecylbenzene) was only50% of run 30. The reactive isomer had apparently been substantiallyexhausted in previous runs.

From run 32, Table V, 26 grams of a brown paste similar to thatpreviously described, was obtained. The surface-active properties ofthis paste were evaluated by dissolving 2.61 grams per liter in benzene.The interfacial tension (benzene/H2O) was 6.3 dynes/cm., in comparisonto 27.3 dynes/cm. for pure benzene. The surface tension (air-liquid) ofthis solution was 26.2 dynes/cm. in comparison to 28.2 dynes/cm. forpure benzene. Further tests with this product also indicated that it wasefiective for increasing the viscosity index of various lube oils.

The effect of temperature upon the reaction is shown in run 33, carriedout at 34 C. Here the conversion of dodecylbenzene was severalfoldgreater than from similar runs at 0 C. This indicates that even the morerefractory isomers of the dodecylbenzene react at elevated temperature.The product in physical appearance and the composition was similar tothe 0 C. material. A portion of the product was hydrogenatedcatalytically with 5 grams of a nickel-kieselguhr catalyst at 100 C.under 100 atmospheres of hydrogen pressure. The results demonstratedthat 320 ml. of hydrogen per gram were absorbed.

One gram of the water-insoluble-ether-soluble product boiling abovedodecylbenzene from run 32 was added to 40 ml. of concentrated nitricacid at 0 C. 40 m1. of concentrated sulfuric acid was then addeddropwise at 0 C., the sample dissolved slowly. After standing 20 hoursat 25 C.,.ice was added to precipitate out a yellow product. This waswater washed, dried, and on analysis for nitrogen was found to contain5.28% nitrogen.

EXAMPLE XIII The pentaacetate of l,l-di-p-tolyl-l-desoxy-D-glucitol wasprepared by heating the ditolyl glucitol with acetic anhydride in thepresence of sodium acetate.

One gram of the ester obtained was then added to 40 ml. of concentratednitric acid at 0 C. The 40 ml. of concentrated sulfuric acid were addeddropwise. The ester went into solution slowly. The mixture was allowedto stand for 3 hours at a temperature not exceeding 25 C., after whichtime it was poured on to ice. The white precipitate which separated wasremoved by filtration, then recrystallized from n-heptane. The nitrogencontent of this product was found to be 6.28% The product underwentdecomposition when exposed to the atmosphere for several days, changingin color from white to yellowish brown. When kept in a desiccator,decomposition was considerably retarded.

In a separate experiment, one gram of the ester was added to a solutionof one gram of potassium nitrate in 30 ml. of concentrated sulfuricacid. The ester went into solution slowly. The mixture was allowed tostand for one-half hour at approximately 30 C., after which time it waspoured onto ice. The white precipitate which separated was removed byfiltration and washed well with water. After standing for several daysexposed to the atmosphere, the white solid changed in appearance to ayellow-brown syrupy material.

EXAMPLE XIV The following experiments were conducted to obtain data inregard to the constitution of the products and the progressive reactionsof the various products in the glucose-toluene-hydrogen fluoridereaction system, and to determine the effect of contact time upon thereaction of toluene with glucose or cellulose at the two temperatures, 0C. and 30 C. The procedure utilized inthis example is similar to thatdescribed in Examples VII and VIII. A summary of the results obtained isgiven in the following 3 tables:

Table VI.Reacti0n of glucose with toluene in the presence of hydrogenfluoride at 0 C.

Charge: Grains d-Glucose 50 Toluene 170 Hydrogen fluoride M 220: ;15

Run No 34 35 36 37 38 30 Contact Time, Hrs 0.5 0. 5 3 5 20 66 Recovery,Grams:

Water-Soluble 25 C 66 46 26 25 11 Water-Insoluble 25 C-.. 13 9 34 59 6983 Pentane-Soluble 1 1 Total Toluene-Free Organic. 75 9t 91 TolueneReacted, Grams 25 30 35 44 4'1 Ratio, Mols Toluene/Mols Glucose 1.01.2 1. 4 1.8 1.8

Characterized Products, Grams:

Presumed present; not isolated. b Identified in small amounts; yieldunknown.

Table VII.Reacti0n of glucose with toluene in the presence of hydrogenfluoride at 30 C.

Charge: Grams Glucose 50 Toluene Hydrogen fluoride 2203:15

Run N 0 40 41 42 43 44 45 Contact Time, Hrs 0. 5 1. 5 3 20 2O 66Recovery Grams:

Water-Soluble 25 C 31 2G 11 30 24 13 Water-Insoluble 25 C- 47 55 72 7881 93 Pentane-Soluble 3 25 45 Total Toluene-Free Organic. 78 81 83 108108 10G Toluene Reacted, Grams 28 31 33 58 58 56 Ratio, MolsToluene/Mols Glucose 1.1 1. 3 1.3 2. 3 2. 3 2. 2 Characterized Products,Grams:

Present; concentration not determined.

presence of hydrogen fluoride at C.

Charge: Grams Oellulose 50 Toluene. 170 Hydrogen fluoride 220:1:15

Run No 46 47 48 Contact Time, Hrs 0. 3 20 Recovery, Grams:

Water-Soluble 25 0 53 43 42 Water-Insoluble 25 0 5 44 68 Pentane-Soluble1 Total Toluene-Free Organic 68 87 110 Toluene Reacted, Grams 8 37 60Ratio, Mols Toluene/Mole Cell 0.3 1 4 2. 3

Characterized Products, Grams:

A 4 26 20 B 0 0 0 D 1 Presumed present; not isolated.

From Tables VI, VII, and VIII it will be noted that the reactionproducts of glucose and of cellulose with toluene are the same and aredependent upon temperature and contact time. The four reaction productsobserved are referred to in the table as A, B, C, and D. The propertiesof these products are as follows:

(Previously identified as 1,1-ditolyl-1-desoxy-D- glucitol)1,4-dicarboxybenzophenone.

Crystalline form: Usually amorphous gel.

Occasionally needles. Melting point: 212-215 C. Empirical formula:CrsHmOs. Solubility:

Water, moderately soluble at 20 C. Alcohol, soluble cold. Ethyl acetate,soluble. Ether, insoluble. Chromic acid oxidation products:

No terephthalic acid. No 4,4-dicarboxybenzophenone.

Crystalline form: yellow amorphous granules. Melting point: 7080 C.Solubility:

Water at 100 C., insoluble. Ether, very soluble. Benzene, soluble cold.Acetone, very soluble. Generally soluble in warm aliphatic hydrocarbons.

Chromic acid oxidation product: terephthalic acid.

(A viscous oil, deep red color, pentane soluble) Elementary analysis:

Percent carb Percent hydrog Molecular weight, 394 (found cryoscopically)Chromic acid oxidation product: mostly terephthalic acid, some smallamounts of 4,4'-dicarboxybenzophenone.

Another product isomeric with B above has also been noted in manyexperiments, although it has never been obtained in pure form. Forsimplification of the following discussion it will be referred to asproductE and is characterized as follows:

From an examination of the foregoing tables, the following conclusionshave been deduced:

(1) At 0 or 30 C., the amount of toluene which reacts with glucose orcellulose increases with time up to about 20 hours after which, althoughmore toluene may not enter the reaction, the nature of the productcontinues to change.

(2) At 0 C., product A reaches a. maximum in the time range of fromabout 3 to about 20 hours, then falls off.

(3) At 30 0, product A is present in appreciable amounts at shortcontact times; it falls off in amounts approaching almost nothing atlong contact times.

(4) Product B is found at 0 C. only after long contacting; at 30 C., itwas found at all times studied in about the same amounts.

(5) Product C was not identified from runs at 0 C. At 30 C., it soonbecame the principal product.

(6) Product D, the hydrocarbon oil, appears after about 3 hours time andthen steadily increases with time.

(7) Cellulose and glucose give nearly identical reaction products, withthe exception that at the shortest time studied (0.5 hour), less toluenereacted with cellulose than with glucose, probably due to a time lag inthe breaking down of cellulose into glucose units.

EXAMPLE XV In view of the information obtained in the preceding exampleson the reaction of glucose or fructose with toluene in the presence ofhydrogen fluoride, an extension of this reaction was conducted bycontacting sucrose and molasses with toluene in the presence of hydrogenfluoride. Sucrose is a D glucopyranosyl B D fructo-furanoside, which isa nonreducing dihexose. Sucrose, on the basis of previous reactionsstudies, should hydrolyze and yield a glucose and a fructose residue.These monosaccharides should then react with toluene yielding compoundssimilar to those already obtained independently from glucose and fromfructose as set forth in previous examples. The procedure utilized inthis example for the reaction and working up the products is similar tothat described previously. A summary of the results obtained is given inthe following table:

as Table IX.-Reac!ion of sucrose or molasses with toluene in thepresence of hydrogen fluoride at C.

Oh arge: Grams Carbohydrate 50 Toluene 170 Hydrogen fluoride 2203:

Carbohydrates Used Sucrose Molasses Run No 49 50 51 52 53 Contact Time,Hrs 0. 5 3 20 66 Recovery, Grams:

Water-soluble at 0 44 38 20 16 10 Water-insoluble at 25 0-- 13 68 65 84Pentane-soiuble- 1 2 5 2 Total toluene-free orga 57 78 83 81 94 TolueneRoasted, grams... 7 28 .33 31 44 Ratio,molstoluene/molscarb 0. 3 1. 1 1.3 1. 3 1. 8

Characterized Products grams:

Presumed present; not isolated. b Identified in small amounts; yieldunknown.

Products A, B, and C have been described fully in Example XIV. ProductP, which is a compound of a formula CmHraOs, has been describedpreviously in Example VIII and is believed to have the followingstructure:

CHnOH compounds formed from glucose or fructose reacting alone.Compounds A and B were isolated in yields which indicate that conditionscan be found for reacting sucrose to give substantial conversions tothem. As Was expected from the earlier work on fructose alone, product Gdid not appearin appreciable quantities unless long contacting timeswere used.

The virtual absence of fructose in the reaction at times up to threehours, at which time glucose is completely reacted with toluene, showsthat the subject reaction, that is of sucrose with toluene, can becarried out to achieve, in efiect, a separation of glucose and fructoseunits in sucrose by the conversion at short contact times of glucoseinto alkylated derivatives without substantially reacting fructoseunits.

The molasses used in runs 52 and S3 was a dry variety having thefollowing approximate composition: sucrose, 52%; invert sugar, 25%;protein, 4%; ash, 10%; water and nonsugar organic material, 9%. Thecondensation of molasses with toluene was studied using 20 and 66 hourcontacting times. From the former run, small amounts of compounds A andG were isolated, but from the 66 hour run, no chemical individual wasisolated although the recovery of total toluene-free organic productindicated that a very substantial amount of toluene had entered into thereaction.

EXAMPLE XVI In Example XIV, it was shown that the reaction of glucoseand toluene gave -a pentane-soluble oil after long contacting at 30 C.This pcntane-soluble oil in some instances became the principal product.It has been referred to as product D, a red viscous pentane-soluble oil.This example describes the characteristics of this product D fromvarious reactants.

The experiments were carried out in a procedure similar to thatpreviously described except that the temperature utilized was 30 C. sothat maximum yields of the de sired pentane-soluble product wereobtained.

The reactants and conditions utilized, and the products obtained aresummarized in the following two tables:

Table X .Condensation of aromatics with carbohydrates at 30 C.

Run No 54 5s 56 57 as 59 so I Contact Time, Hours. 108 as 70 s 24 so asH ..Q 0H Charge, Grams:

glucgse 5(0) 58 70 5O 50 100 7 rue 050.. 5 0 0 0 0 H OH 50 gelllzellfln17 5 175 265 178 0 c 0 v o ueue O 170 3 4 H C OH Hydrogen Fluoride 242231 347 242 224 235 333 I Recovery, Grams: H Pentanefioluble... 3.4 2.613.2 3 30.5 45 83.5 Benzene-Soluble Chromrc acid oxidation of thiscompound yielded 4,4 -d1- gl ntane-Insolucarboxybenzophenone. Thissubstance melts at 210 C. j' 'af 19f i2 1:: From the results obtained itcan be seen that sucrose g gg e- 166-6 was reacted with toluene atvarying contact times. The fi 3,,,, 59 go 83 110, 5 products showed thatthe reaction mixture contained the Table Xl.C0ndensation of aromaticswith carbohydrates at 30 C.

Run No 61 62 63 64 65 66 e7 68 69 Contact Time, Hours Oharbc, Grams:

Glucose Fructose Toluene Isobutane Hydrogen Fluoride Recovery, Grams:

Pentane-Soluble Benzene-Soluble (Pentane- Insoluble) ater-SolubleToluene Total Toluene-Free Organic.

Melting Percent Percent Point, Carbon Hydrodeg-rees gen Found fortriphenylmethane 90. -92 93. O7 6. 81 Pure triphenylmethane 92 93. 40 6.60

Runs 55 and 56, Table X, gives the results of the reaction of benzeneand fructose. These results indicate that benzene reacts diflicultlywith fructose under the conditions outlined. When 75 grams of fructosewas contacted for 70 hours with an excess of benzene in the presence ofhydrogen fluoride (run 56), 13.2 grams of pentane-soluble was obtained.This pentane-soluble portion of the reaction product was distilled atreduced pressure and on infrared analysis of distillate cuts was shownto contain over 60% diphenylmethane. There was an indication thattriphenylmethane was also present.

In Table X, runs 57, 58, and 59, were made using 50 grams of glucose, anexcess of toluene, and under similar conditions except for increasingperiods of reaction. The pentane-soluble portion of the reaction productincreased with time as follows: 3 hours, 3 grams; 24 hours, 30 grams;and 66 hours, 45 grams. From run 60, the pentane-soluble portion of thereaction product was distilled at atmospheric pressure. The fractionboiling from 280-340 C. (5.9 grams) was redistilled under vacuum anddi-p-tolylmethane identified therefrom. A substantially light yellowcrystalline compound, melting point 220 C., and boiling near 400 C. at760 mm. was also isolated. It contained 92.4% carbon and 7.0% hydrogenwhich is compatible with the theoretical carbon and hydrogen analysis oftri-p-tolylmethane which boils at about 400 C. An extensive plateau near500 C. consisting of a red glass of molecular weight near 350 was alsoobtained.

The reaction of toluene with fructose to produce pentane-solublematerial, Table XI, runs 61, 62, 63, 66, and 67, was thoroughlyinvestigated. Although previous examples have indicated that thefructose-toluene reaction at 0 C. was markedly slower than thecorresponding glucose reaction, in contrast, at 30 C., thepentanesoluble product appearance was markedly faster from fructose thanfrom glucose. Also, the yield of the pentane-insoluble product tended toreach a constant amount at about 24-66 hours time. A vacuum distillationof the pentane-soluble product from these runs resulted in productssimilar to those from glucose and toluene. Di-p-tolylmethane wasidentified. Two pure compounds boiling near 400 C. were also isolated.One, light, yellow crystals, had a melting point of 230231.5 andcontained 92.80% carbon and 7.40% hydrogen. The other consisted of whitecrystals with a light purple fluorescence which had a melting point of139l40 C. and an elementary analysis of 93.10% carbon and 7.0% hydrogen.The material boiling on a plateau near 500 C. was a red glass with amolecular weight around 350. On oxidation it yielded terephthalic acid.

Runs 64 and 65, Table XI, were carried out by reacting toluene andfructose in the presence of isobutane. The hydrocarbon part of theproduct appeared to correspond to that observed in the absence ofisobutane except for the presence of tert-butyltoluene (a 2:1 mixture ofmeta to para), and another compound believed to be tert-butylateddi-p-tolylmethane. This latter compound consisted of White crystalswhich melted at 80- 81 C. and contained 91.1% carbon and 8.8% hydrogen.

The reaction of ethylbenzene with glucose, runs 68 and 69, Table XI,gave yields of pentane-soluble products similar to those yields obtainedfrom toluene and glucose under similar conditions. Twenty-six percent ofthe pentane-soluble product (36 grams) from run 69, boiled in the range300335 C. Two separate plateaus were observed. From one plateau,di-p-ethylphenylmethane was isolated. Its oxidation product is 4,4-dicarboxybenzophenone. Its boiling point, 320 C., its refractive index,elementary analysis (C, 91.04%; H, 9.29%), and molecular weight, 224.3corresponding to the proper structural formula. Also,l-p-ethylphenyl-lphenylethane was isolated. Its oxidation product ispbenzoyl benzoic acid which was identified through its methyl ester. Theboiling point 300-304 C. refractive index, elementary analysis (C,91.33%; H, 8.88%), molecular weight, 210.3, and oxidation product are inaccordance with the proper structural formula.

Part of the total pentane-soluble hydrocarbons from runs 66 and 62,Table XI, were combined and their effect on the viscosity index oflubricating oils evaluated. A SAE-40 lubricating oil with no additiveshad a specific gravity of 0.875 and a viscosity index of 88.5. With 1%of added pentane-soluble hydrocarbons, its viscosity index was reducedto 84.1, and with 3% of added pentane-soluble hydrocarbons, thisviscosity index was reduced to 80.0.

EXAMPLE XVII This example illustrates the reaction of toluene withalginic acid. Alginic acid is a polysaccharide composed of uronic acidunits. This reaction was studied at 0 C. in three different experimentswhich involve the utilization of hydrogen fluoride as the catalyst. Intwo of the experiments, the contacting was for a period of two hourstime, while in the third experiment a reaction time of 16 hours wasutilized.

EXPERIMENT I The following reactants were charged to an 1100 ml.turbomixer autoclave: 50 grams of alginic acid, 172 grams of toluene,and 226 grams of HP. The mixture was contacted for 2 hours at 0 C. andatmospheric pressure. At the end of the contact time, most of thehydrogen fluoride was flushed from the system by passing a stream ofnitrogen through the autoclave. The product, which was transferred to asilver dish, weighed 129 grams after standing overnight in a hood-draft.

A portion of the product (30 grams) was washed twice with cold water andthen heated to the boiling point of water with another portion of water.The hot water was decanted and on cooling yielded a syrupy white coloredprecipitate. A small portion of the syrupy white precipitate wasoxidized and from the oxidation product was obtained1,4-dicarboxybenzophenone which was identified by the melting point ofits dimethyl ester. Another portion of the syrupy white precipitate wasextracted with ether and on evaporation of the ether, a glossy residueremained. This residue was dissolved in hot acetone and on cooling, afluffy white precipitate appeared crystalline under a microscope.

EXPERIMENT II This experiment was conducted in a manner similar toExperiment I with grams of alginic acid, 258 grams of toluene, and 413grams of HF. These reactants were contacted for 2 hours at 0 C. 259grams of product was obtained. After standing several days, the productweighed grams, indicating that it still contained considerable hydrogenfluoride after the initial nitrogen purge. This product was dissolved indilute sodium hydroxide solution. A portion of the caustic solution wasacidified and a precipitate separated. The precipitate was dried byheating with benzene in an evaporating dish. The dry solid was washedwith ether and the ether .then evaporated. The resultant dry solidmelted from 160-180 C. and could not be crystallized from alcohol oracetic acid. The remainder of the caustic solution was then acidifiedwith hydrochloric acid. The syrupy material which separated was washedwith water and dried in a desiccator. A dry powder having aneutralization equivalent of 280 was obtained.

A surface-active material was prepared by exactly neutralizing eightgrams of the powdery material with sodium hydroxide. This solution wasether extracted and the water layer on evaporation yielded 4.1 grams ofa highly surface-active material product.

EXPERIMENT III drying in a desiccator, the net weight of the resultantmaterial was 101 grams. A small portion of this on oxidation yieldedboth terephthalic acid and 1,4dicar boxybenzophenone. The product wasnot soluble in pentane. 20 grams of the product was treated with benzeneand the insoluble portion filtered ofif. Clusters of crystals wereobserved under a microscope.

The benzene insoluble material was boiled with toluene and on cooling acrystalline precipitate appeared. This precipitate had a melting pointof approximately 300 C. and after four recrystallizations from tolueneit melted as follows: from 250 C. and higher, the material graduallyturned brown in color; at 287290 C., the precipitate melted anddecomposed. This product on analysis was found to contain 77.50% carbonand 7.11% hydrogen.

I claim as my invention:

1. A process which comprises reacting a hydrocarbon with a carbohydrateselected from the group consisting of monosaccharides, their desoxyandtheir omegacarboxy-derivatives, oligosaccharides, and polysaccharides inthe presence of a catalytic amount of hydrogen fluoride at a temperatureof from about to about 100 C. to produce a compound selected from thegroup consisting of hydrocarbon substituted desoXy-alditols andhydrocarbon substituted desoxy-ketitols, and recovering said compound.

2. A process which comprises reacting an isoparalfinic hydrocarbon witha carbohydrate selected from the group consisting of monosaccharides,their desoxyand their omega-carboxy-derivatives, oligosaccharides, andpolysaccharides, in the presence of a catalytic amount of hydrogenfluoride at a temperature of from about -10 to about 100 C. to produce acompound selected from the group consisting of hydrocarbon substituteddesoxyalditols and hydrocarbon substituted desoxy-ketitols, andrecovering said compound.

3. A process which comprises reacting an olefinic hydrocarbon with acarbohydrate selected from the group consisting of monosaccharides,their desoxyand their omega-carboxy-derivatives, oligosaccharides, andpolysaccharides in the presence of a catalytic amount of hydrogenfluoride at a temperature of from about --10 to about 100 C. to producea compound selected from the group consisting of hydrocarbon substituteddesoxyalditols and hydrocarbon substituted desoxy-ketitols, andrecovering said compound.

4. A process which comprises reacting an aromatic hydrocarbon with acarbohydrate selected from the group consisting of monosaccharides,their desoxyand their omega-carboxy-derivatives, oligosaccharides, andpolysaccharides in the presence of a catalytic amount of hydrogenfluoride at a temperature of from about -10 to about 100 C. to produce acompound selected from the group consisting of hydrocarbon substituteddesoxyalditols and hydrocarbon substituted desoxy-ketitols, andrecovering said compound.

5. A process which comprises reacting a naphthenic hydrocarbon with acarbohydrate selected from the group consisting of monosaccharides,their desoxyand their omega-carboxy-derivatives, oligosaccharides, andpolysaccharides, in the presence of a catalytic amount of hydrogenfluoride at a temperature of from about 10 to about C. to produce acompound selected from the group consisting of hydrocarbon substituteddesoxyalditols and hydrocarbon substituted desoXy-ketitols, andrecovering said compound.

6. A process which comprises reacting toluene with cellulose in thepresence of a catalytic amount of hydrogen fluoride at a temperature offrom about 0 to about 100 C. to produce a p-tolyl-l-desoxy-glucitol, andrecovering the last-named compound.

7. A process which comprises reacting toluene with glucose in thepresence of a catalytic amount of hydrogen fluoride at a temperature offrom about -10 to about 100 C. to produce a p-tolyl-l-desoxy-glucitol,and recovering the last-named compound.

8. A process which comprises reacting toluene with fructose in thepresence of a catalytic amount of hydrogen fluoride at a temperature offrom about -10 to about 100 C. to produce a p-tolyl-2-desoxy-fructitol,and recovering the last-named compound.

9. A process which comprises reacting toluene with sorbosc in thepresence of a catalytic amount of hydrogen fluoride at a temperature offrom about 10 to about 100 C. to produce a p-tolyl-2-desoxy-sorbitol,and recovering the last-named compound.

10. A process which comprises reacting toluene with sucrose in thepresence of a catalytic amount of hydrogen fluoride at a temperature offrom about 10 to about 100 C. to produce a p-tolyl-l-desoxy-glucitol anda p-tolyl-2-desoxy-fructitol, and recovering the resultant reactionproducts.

11. A process which comprises reacting an aromatic hydrocarbon with amonosaccharide in the presence of a catalytic amount of hydrogenfluoride at a temperature of from about -10 to about 100 C. to produce acompound selected from the group consisting of a hydrocarbon substituteddesoxy-alditol and a hydrocarbon substituted desoxy-ketitol, andrecovering said compound.

12. A process which comprises reacting an aromatic hydrocarbon with adisaccharide in the presence of a catalytic amount of hydrogen fluorideat a temperature of from about 10 to about 100 C. to produce a compoundselected from the group consisting of a hydrocarbon substituteddesoxy-alditol and a hydrocarbon substituted desoxy-ketitol, andrecovering said compound. 13. A process which comprises reacting anaromatic hydrocarbon with a polysaccharide in the presence of acatalytic amount of hydrogen fluoride at a temperature of from about 10to about 100 C. to produce a compound selected from the group consistingof a hydrocarbon substituted desoxy-alditol and a hydrocarbonsubstituted desoxy-ketitol, and recovering said compound.

References Cited in the file of this patent UNITED STATES PATENTS2,252,725 Niederl Aug. 19, 1941 2,379,368 Matuszak June 26, 19452,400,520 Kuhn May 21, 1946 2,404,340 Zimmerman July 16, 1946 2,460,803Bonner et a1. Feb. 8, 1949 2,472,276 Bonner ct a1. June 7, 1949 FOREIGNPATENTS Simons: Ind. and Eng. Chem., vol. 32, pp. 178183, 6 pp.(February 1940).

Thomas: Anhydrous Aluminum Chloride in Organic Chemistry, p. 643 (1 p.),publ. by Reinhold Pub. Corp., New York (1941).

1. A PROCESS WHICH COMPRISES REACTING A HYDROCARBON WITH A CARBOHYDRATESELECTED FROM THE GROUP CONSISTING OF MONOSACCHARIDES, THEIR DESOXY- ANDTHEIR OMEGACARBOXY-DERIVATIVES, OLIGOSACCHARIDES, AND POLYSACCHARIDES INTHE PRESENCE OF A CATALYTIC AMOUNT OF HYDROGEN FLUORIDE AT A TEMPERATUREOF FROM ABOUT -10* TO ABOUT 100* C. TO PRODUCE A COMPOUND SELECTED FROMTHE GROUP CONSISTING OF HYDROCARBON SUBSTITUTED DESOXY-ALDITOLS ANDHYDROCARBON SUBSTITUTED DESOXY-KETITOLS, AND RECOVERING SAID COMPOUND.